US6599638B1 - Colloidally stabilized emulsions - Google Patents

Colloidally stabilized emulsions Download PDF

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US6599638B1
US6599638B1 US09/657,707 US65770700A US6599638B1 US 6599638 B1 US6599638 B1 US 6599638B1 US 65770700 A US65770700 A US 65770700A US 6599638 B1 US6599638 B1 US 6599638B1
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phenolics
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polyvinyl alcohol
phenol
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US09/657,707
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Venkataram Krishnan
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Mallard Creek Polymers Inc
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Dow Reichhold Specialty Latex LLC
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Priority to US10/600,883 priority patent/US20040101700A1/en
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Assigned to MALLARD CREEK POLYMERS, INC. reassignment MALLARD CREEK POLYMERS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOW REICHHOLD SPECIALTY LATEX LLC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/18—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being cellulose or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0464—Impregnants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31779—Next to cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31779—Next to cellulosic
    • Y10T428/31783—Paper or wood

Definitions

  • the present invention relates to colloidally stabilized emulsions, and particularly colloidally stabilized emulsions having reduced or no phenolics.
  • Phenolics e.g., phenol-formaldehyde resins
  • Phenolics have been used as adhesives, laminates, molding materials, paints and the like.
  • phenolics are used in bonding of refractory shapes; fiber bonding such as in filters; felt bonding; binding of friction products such as brake pads; in papermaking; in insulation; in roofing products; and in the binding of foundry sands such as abrasives.
  • filters are used in filters.
  • the filter is provided by impregnating a continuous roll of paper with a phenolic resole in the form of an alcohol solution of a condensate of phenol with formaldehyde.
  • the impregnated and saturated paper is heated to remove the solvent (alcohol) and corrugated to increase surface area.
  • the resin is then cured in an oven and the paper is rolled again.
  • the rolls of the impregnated paper are provided to the filter manufacturer for completion of the process which includes pleating and final curing.
  • Such filters are used in the both air and oil filtering systems in stationary and mobile internal combustion engines.
  • Phenolics however, have disadvantages such as high phenol and formaldehyde levels, brittleness when fully cured, slow curing characteristics, instability and poor shelf life. Moreover, phenolics, particularly water-based phenolics, are difficult to use to impregnate fiber substrates. In such impregnation, co-solvents such as alcohols, must be used and then removed.
  • the present invention provides compositions wherein phenolics are substantially eliminated, substantially reduced or replaced by the use of a colloidally stabilized emulsion polymer.
  • a colloidally stabilized polymer of the invention By using the colloidally stabilized polymer of the invention and eliminating or replacing the use of phenolics, a wide variety of polymers having crosslinkable functionality such as provided by crosslinkers such as epoxies, polyisocyanates, polyurethanes, N-methylol acrylamide, melaminelformaldehyde and the like, can be used or blended together while providing properties comparable to those of polymers having phenolics or of phenolics alone.
  • crosslinkers such as epoxies, polyisocyanates, polyurethanes, N-methylol acrylamide, melaminelformaldehyde and the like
  • the colloidally stabilized emulsion polymers when blended with phenolics, are more stable and compatible with phenolics as compared to surfactant stabilized emulsions.
  • compatibility it is meant that the emulsion polymers, when blended with phenolics, remain stable without coagulating or gelling or becoming a paste over longer periods of time.
  • the blended product can be used over extended periods of time without concern for instability or degradation of performance. Moreover, the need to use undesirable solvents is eliminated.
  • polymers in emulsion form can be colloidally stabilized, particularly with polyvinyl alcohol, and optionally blended with phenolics.
  • Specific polymers in emulsion form include polyvinylacetate, vinylacetate-ethylene(VAE), vinyl acrylics, epoxies, urethanes, acrylics, styrene acrylics, butadiene copolymers, and hybrid emulsions of combinations of the foregoing.
  • VAE vinylacetate-ethylene
  • vinyl acrylics vinyl acrylics
  • epoxies vinyl acrylics
  • urethanes acrylics
  • acrylics styrene acrylics
  • butadiene copolymers butadiene copolymers
  • hybrid emulsions of combinations of the foregoing The present invention can be used in systems to replace phenolics wherein phenolics are used alone, or can be used in systems wherein phenolics are used with other polymers. In the latter, the phenolics can be substantially eliminated or can
  • emulsion polymers that have high levels (i.e., greater than about 15 percent by weight) of nitrogen-containing monomers such as acrylonitrile.
  • nitrogen-containing monomers such as acrylonitrile.
  • the phenols employed in the formation of the phenolic resins generally include any phenol which as heretofore been employed in the formation of phenolic resins and which are not substituted at either the two ortho positions or at the one ortho and the para position. Such unsubstituted positions are necessary for the polymerization reaction to occur.
  • Substituted phenols employed in the formation of the phenolic resins include: alkyl substituted phenols, aryl-substituted phenols, cycloalkyl-substituted phenols, alkenyl-substituted phenols, alkoxy substituted phenols, aryloxy substituted phenols, and halogen-substituted phenols.
  • Suitable phenols include: phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 3-4-xylenol, 3,4,5-trimethylphenol, 3-ethyl phenol, 3,5-diethyl phenol, p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octyl phenol, 3,5-dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxy phenol, 3,4,5-trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol, 3-methyl-4-methyoxy phenol, and p-phenoxy phenol.
  • the aldehydes reacted with the phenol component can include any of the aldehydes heretofore employed in the formation of phenolic resins and include, for example, formaldehyde, and benzaldehyde.
  • the aldehydes employed have the formula R′CHO wherein R′ is a hydrogen or hydrocarbon radical of 1-8 carbon atoms.
  • R′ is a hydrogen or hydrocarbon radical of 1-8 carbon atoms.
  • a particularly preferred phenolic is Resafen 8121 available from Resana, Sao Paulo, Brazil.
  • Suitable aliphatic conjugated dienes are C 4 to C 9 dienes and include, for example, butadiene monomers such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and the like, such as described in U.S. Pat. No. 5,900,451 to Krishnan et al., the disclosure of which is incorporated herein by reference in its entirety. Blends or copolymers of the diene monomers can also be used.
  • the aliphatic conjugated diene is used in an amount, based on total weight of the starting monomers, from about to 1 to about 99 percent by weight, preferably from about 5 to about 30 percent by weight, and most preferably from about 5 to about 15 percent by weight.
  • a particularly preferred aliphatic conjugated diene is 1,3-butadiene.
  • Suitable non-aromatic unsaturated monocarboxylic ester monomers include acrylates and methacrylates.
  • the acrylates and methacrylates may include functional groups such as amino groups, hydroxy groups, epoxy groups and the like.
  • Exemplary acrylates and methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, isobutyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxybutyl methacrylate, n-propyl methacrylate and the like.
  • Exemplary amino-functional methacrylates include t-butylamino ethyl methacrylate and dimethylamino ethyl methacrylate.
  • Suitable non-aromatic dicarboxylic ester monomers are dialkyl fumarates, itaconates and maleates, with the alkyl group having two to eight carbons, with or without functional groups. Specific monomers include diethyl and dimethyl fumarates, itaconates and maleates.
  • Other suitable non-aromatic dicarboxylic ester monomers include di(ethylene glycol) maleate, di(ethylene glycol) itaconate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, and the like.
  • the non-aromatic unsaturated mono- or dicarboxylic ester monomer is used in an amount, based on total weight of the starting monomers, preferably from about 5 to about 95 percent by weight, and most preferably from about 20 to about 80 percent by weight.
  • a particularly preferred non-aromatic unsaturated monocarboxylic ester monomer is methyl methacrylate.
  • aromatic unsaturated monomers may be used and include, but are not limited to, styrene and styrene derivatives such as alphamethylstyrene, p-methyl styrene, vinyltoluene, ethylstyrene, tert-butyl styrene, monochlorostyrene, dichlorostyrene, vinyl benzyl chloride, fluorostyrene, alkoxystyrenes (e.g., paramethoxystyrene) and the like. Mixtures of the above may be used.
  • styrene is employed.
  • the aromatic unsaturated monomer is preferably used from about 5 to about 95 percent based on the total monomer weight, and more preferably from about 20 to about 80 percent by weight.
  • Exemplary nitrogen-containing monomers which may be used include, for example, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide. Acrylonitrile is preferred. Mixtures of the above may be used.
  • the nitrogen-containing monomer is preferably used, for example, in an amount ranging from about 5 to about 95 percent based on the total weight of the monomers, and more preferably from about 15 to about 80 percent by weight.
  • Known and conventional protective colloids may be employed in the emulsion polymer such as partially and fully hydrolyzed polyvinyl alcohols; cellulose, ethers, e.g., hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, starch ad start derivatives, carboxymethyl cellulose (CMC); the natural and synthetic gums, e.g., gum tragacanth and gum Arabic, polyacrylic acid; acrylates; poly(vinyl alcohol)co(vinyl amine) copolymers and the like.
  • CMC carboxymethyl cellulose
  • Partially and fully hydrolyzed polyvinyl alcohols such as those available from Air Products, sold under the trademark AirvolTM are preferred and are preferably employed from about 0.1 to about 10 percent based on the weight of the total monomer, more preferably from about 0.5 to 5 percent, and most preferably from about 1 to about 4 percent.
  • a polymerizable surfactant which contains ethylenic unsaturation is used and is copolymerized with the other monomers during emulsion polymerization.
  • the surfactant is incorporated in to the backbone of the polymer and serves to stabilize the latex.
  • suitable surfactants containing ethylenic unsaturation are provided in U.S. Pat. No. 5,296,627 to Tang et al., the disclosure of which is incorporated by reference herein in its entirety.
  • polymerizable surfactants are also described in U.S. Pat. No. 5,900,451 to Krishnan et al.
  • a preferred polymerizable surfactant is SAM 186NTM sold by PPG Industries, Inc. of Pittsburgh, Pa.
  • the polymerizable surfactant may be used in various amounts.
  • the stabilized emulsion polymer may include between about 0.1 and about 5 percent polymerizable surfactant based on the monomer weight, more preferably from about 1 to about 4 weight percent, and most preferably from about 2 to about 3 weight percent.
  • surfactants may be used in conjunction with the surfactant having ethylenic unsaturation described herein.
  • Such surfactants are preferably of the anionic and nonionic type.
  • the selection of these surfactants is apparent to one skilled in the art.
  • Preferred nonionic surfactants are selected from the family of alkylphenoxypoly(ethyleneoxy) ethanols where the alkyl group typically various from C 7 -C 18 and the ethylene oxide units vary from 4-100 moles.
  • Various preferred surfactants in this class include the ethoxylated octyl and nonyl phenols, and in particular ethoxylated nonyl phenols with a hydrophobic/lipophilic balance (HLB) of 15-19.
  • HLB hydrophobic/lipophilic balance
  • Non-APE (alkylphenol ethoxylate) surfactants such as ethoxylated alcohols, for example, Abex 2525, are also preferred.
  • Anionic surfactants can be selected from the broad class of sulfonates, sulfates, ethersulfates, sulfosuccinates, diphenyloxide disulfonates, and the like, and are readily apparent to anyone skilled in the art.
  • An unsaturated mono- or dicarboxylic acid monomer may also be included in the stabilized emulsion polymer. These monomers include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. Derivatives, blends, and mixtures of the above may also be used.
  • the unsaturated mono- or discarboxylic acid monomer may be used in an amount ranging from about 0 to about 15 percent based on the total monomer weight, and more preferably from about 0 to about 5 weight percent.
  • Additional comonomers can be added to the stabilized emulsion polymer. Included among such additional comonomers are monoethylenically unsaturated substituted aliphatic hydrocarbons such as vinyl chloride, and vinylidene chloride; aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl butyrate, vinyl versatate and vinyl neodecanoate.
  • monoethylenically unsaturated substituted aliphatic hydrocarbons such as vinyl chloride, and vinylidene chloride
  • aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl butyrate, vinyl versatate and vinyl neodecanoate.
  • the stabilized emulsion polymer can include additives to enhance its various physical and mechanical properties; the selection of which is readily apparent to one skilled in the art.
  • crosslinking agents can be included such as vinylic compounds (e.g., divinyl benzene); allyllic compounds (e.g., allyl methacrylate, diallyl maleate); multifunctional acrylates (e.g., di, tri and tetra (meth)acrylates); self-crosslinking monomers such as N-methylol acrylamide, N-methylol methacrylamide and C 1 to C 4 ethers of these monomers respectively (e.g., N-iso[butoxymethoxy] methacrylamide), acrylamido glycolic acid and its esters, and alkyl acrylamido glycolate alkyl ethers (e.g., methylacrylamido glycolate methyl ether).
  • vinylic compounds e.g., divinyl benzene
  • allyllic compounds e
  • the crosslinking agents can be included in amounts of up to about 15 percent by weight, and preferably from about 3 to about 8 percent by weight. Additional monomers such as silanes can be included to improve specific properties such as latex stability, solvent resistance, as well as adhesion and strength and are described, for example, in U.S. Pat. No. 5,830,934 to Krishnan, the disclosure of which is incorporated herein by reference in its entirety.
  • Initiators which facilitate polymerization are typically used and include, for example, materials such as persulfates, organic peroxides, peresters, and azo compounds such as azobis(isobutyronitrile) (AIBN).
  • Persulfate initiators are preferred and include, for example, potassium persulfate and ammonium persulfate.
  • Reductants may be employed in the polymerization, and are typically employed in combination with the initiator as part of a redox system.
  • Suitable reductants include sodium bisulfite, erythorbic acid, ascorbic acid, sodium thiosulfate, sodium formaldehyde sulfoxylate (SFS), and the like.
  • additives which may be used include other natural and synthetic binders, fixing agents, wetting agents, plasticizers (e.g., diisodecyl phthalate), softeners, foam-inhibiting agents, froth aids, other crosslinking agents (e.g., melamine formaldehyde resin, epoxies, polyisocyanates, etc.), flame retardants, dispersing agents (e.g., tetrasodium pyrophosphate), pH adjusting components (e.g., ammonium hydroxide), sequestering or chelating agents (e.g., ethylene diaminetetraacetic acid (EDTA)) and other components.
  • binders fixing agents, wetting agents, plasticizers (e.g., diisodecyl phthalate), softeners, foam-inhibiting agents, froth aids, other crosslinking agents (e.g., melamine formaldehyde resin, epoxies, polyiso
  • One use of the reduced phenolic/butadiene blend is, for example, the fabrication of filters (e.g., oil filters).
  • filters e.g., oil filters.
  • a continuous roll of paper is conventionally impregnated with the binder in the form of an alcohol solution.
  • the saturated paper is heated to remove the alcohol (solvent).
  • the alcohol solution is not needed and this step is eliminated.
  • the treated paper is then corrugated for the purpose of increasing surface area.
  • the corrugated sheet is subsequently conveyed through an oven in order to advance the cure of the resinous impregnate to a fusible intermediate or B stage, and then the corrugated sheet is made into a filter.
  • a polyvinyl alcohol stabilized butadiene emulsion comprising the following:
  • Example 1 The testing was done on No. 4 Whatman Filter Paper. Each sheet had a 20 percent add on of the composition of Example 1 is diluted to 22 percent total solids, was dried for 4 minutes at 225° F. and was allowed to condition overnight in a constant temperature/humidity room. Then each sheet was cured at 350° F. in a forced air oven for the cure times of the tables.
  • Example 1 Various amounts a phenolic available as Resafen 8121 from Resana, Sao Paulo Brazil, were added to Example 1, along with phenolic only, and the tensile strengths measured. The amounts added are as follows:
  • a polyvinyl alcohol stabilized emulsion having more N-methylol acrylamide and no butylacrylate comprising the following:
  • compositions having no phenolic or reduced phenolic can provide physical properties comparable to conventional emulsion compositions having phenolics.

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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Abstract

A filter substrate impregnated with an emulsion polymer, the emulsion polymer being substantially devoid of phenolics and stabilized using a protective colloid.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
The instant application claims priority to U.S. Provisional Application Ser. No. 60/153,441 filed Sep. 10, 1999, the disclosure of which is incorporated herein by reference in its entirety.
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates to colloidally stabilized emulsions, and particularly colloidally stabilized emulsions having reduced or no phenolics.
Phenolics (e.g., phenol-formaldehyde resins), have been used as adhesives, laminates, molding materials, paints and the like. Of particular interest is the use of phenolics as adhesives or binders in non-woven substrates and papers. More specifically, phenolics are used in bonding of refractory shapes; fiber bonding such as in filters; felt bonding; binding of friction products such as brake pads; in papermaking; in insulation; in roofing products; and in the binding of foundry sands such as abrasives. Of particular interest is the use of phenolics in filters. Typically, the filter is provided by impregnating a continuous roll of paper with a phenolic resole in the form of an alcohol solution of a condensate of phenol with formaldehyde. The impregnated and saturated paper is heated to remove the solvent (alcohol) and corrugated to increase surface area. The resin is then cured in an oven and the paper is rolled again. The rolls of the impregnated paper are provided to the filter manufacturer for completion of the process which includes pleating and final curing. Such filters are used in the both air and oil filtering systems in stationary and mobile internal combustion engines.
Phenolics, however, have disadvantages such as high phenol and formaldehyde levels, brittleness when fully cured, slow curing characteristics, instability and poor shelf life. Moreover, phenolics, particularly water-based phenolics, are difficult to use to impregnate fiber substrates. In such impregnation, co-solvents such as alcohols, must be used and then removed.
To this end, it would be desirable to substantially eliminate, or in the alternative, substantially reduce the amount of phenolics used in products and with substrates wherein phenolics have traditionally been used as binders or adhesives.
SUMMARY OF THE INVENTION
The present invention provides compositions wherein phenolics are substantially eliminated, substantially reduced or replaced by the use of a colloidally stabilized emulsion polymer. By using the colloidally stabilized polymer of the invention and eliminating or replacing the use of phenolics, a wide variety of polymers having crosslinkable functionality such as provided by crosslinkers such as epoxies, polyisocyanates, polyurethanes, N-methylol acrylamide, melaminelformaldehyde and the like, can be used or blended together while providing properties comparable to those of polymers having phenolics or of phenolics alone.
Alternatively, the colloidally stabilized emulsion polymers, when blended with phenolics, are more stable and compatible with phenolics as compared to surfactant stabilized emulsions. By compatibility, it is meant that the emulsion polymers, when blended with phenolics, remain stable without coagulating or gelling or becoming a paste over longer periods of time. Thus, the blended product can be used over extended periods of time without concern for instability or degradation of performance. Moreover, the need to use undesirable solvents is eliminated.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be described more fully hereinafter, in which preferred embodiments of the invention are shown. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
It is believed that a wide variety of polymers in emulsion form can be colloidally stabilized, particularly with polyvinyl alcohol, and optionally blended with phenolics. Specific polymers in emulsion form include polyvinylacetate, vinylacetate-ethylene(VAE), vinyl acrylics, epoxies, urethanes, acrylics, styrene acrylics, butadiene copolymers, and hybrid emulsions of combinations of the foregoing. The present invention can be used in systems to replace phenolics wherein phenolics are used alone, or can be used in systems wherein phenolics are used with other polymers. In the latter, the phenolics can be substantially eliminated or can be substantially reduced.
Of particular interest are emulsion polymers that have high levels (i.e., greater than about 15 percent by weight) of nitrogen-containing monomers such as acrylonitrile. By being able to increase the level of acrylonitrile, properties such as oil and grease resistance can be improved without adversely affecting the physical properties contributed to by the phenolics.
As stated above, it is desirable to substantially eliminate the use of phenolics; however, phenolics may still be used at a reduced level. The phenols employed in the formation of the phenolic resins generally include any phenol which as heretofore been employed in the formation of phenolic resins and which are not substituted at either the two ortho positions or at the one ortho and the para position. Such unsubstituted positions are necessary for the polymerization reaction to occur. Substituted phenols employed in the formation of the phenolic resins include: alkyl substituted phenols, aryl-substituted phenols, cycloalkyl-substituted phenols, alkenyl-substituted phenols, alkoxy substituted phenols, aryloxy substituted phenols, and halogen-substituted phenols. Specific examples of suitable phenols include: phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 3-4-xylenol, 3,4,5-trimethylphenol, 3-ethyl phenol, 3,5-diethyl phenol, p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octyl phenol, 3,5-dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxy phenol, 3,4,5-trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol, 3-methyl-4-methyoxy phenol, and p-phenoxy phenol.
The aldehydes reacted with the phenol component can include any of the aldehydes heretofore employed in the formation of phenolic resins and include, for example, formaldehyde, and benzaldehyde. In general, the aldehydes employed have the formula R′CHO wherein R′ is a hydrogen or hydrocarbon radical of 1-8 carbon atoms. A particularly preferred phenolic is Resafen 8121 available from Resana, Sao Paulo, Brazil.
With respect to the polymers, of particular interest are the ones with aliphatic conjugated dienes. Suitable aliphatic conjugated dienes are C4 to C9 dienes and include, for example, butadiene monomers such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and the like, such as described in U.S. Pat. No. 5,900,451 to Krishnan et al., the disclosure of which is incorporated herein by reference in its entirety. Blends or copolymers of the diene monomers can also be used. The aliphatic conjugated diene is used in an amount, based on total weight of the starting monomers, from about to 1 to about 99 percent by weight, preferably from about 5 to about 30 percent by weight, and most preferably from about 5 to about 15 percent by weight. A particularly preferred aliphatic conjugated diene is 1,3-butadiene.
Suitable non-aromatic unsaturated monocarboxylic ester monomers include acrylates and methacrylates. The acrylates and methacrylates may include functional groups such as amino groups, hydroxy groups, epoxy groups and the like. Exemplary acrylates and methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, isobutyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxybutyl methacrylate, n-propyl methacrylate and the like. Exemplary amino-functional methacrylates include t-butylamino ethyl methacrylate and dimethylamino ethyl methacrylate. Suitable non-aromatic dicarboxylic ester monomers are dialkyl fumarates, itaconates and maleates, with the alkyl group having two to eight carbons, with or without functional groups. Specific monomers include diethyl and dimethyl fumarates, itaconates and maleates. Other suitable non-aromatic dicarboxylic ester monomers include di(ethylene glycol) maleate, di(ethylene glycol) itaconate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, and the like.
The non-aromatic unsaturated mono- or dicarboxylic ester monomer is used in an amount, based on total weight of the starting monomers, preferably from about 5 to about 95 percent by weight, and most preferably from about 20 to about 80 percent by weight. A particularly preferred non-aromatic unsaturated monocarboxylic ester monomer is methyl methacrylate.
Various aromatic unsaturated monomers may be used and include, but are not limited to, styrene and styrene derivatives such as alphamethylstyrene, p-methyl styrene, vinyltoluene, ethylstyrene, tert-butyl styrene, monochlorostyrene, dichlorostyrene, vinyl benzyl chloride, fluorostyrene, alkoxystyrenes (e.g., paramethoxystyrene) and the like. Mixtures of the above may be used. Preferably, styrene is employed. The aromatic unsaturated monomer is preferably used from about 5 to about 95 percent based on the total monomer weight, and more preferably from about 20 to about 80 percent by weight.
Exemplary nitrogen-containing monomers which may be used include, for example, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide. Acrylonitrile is preferred. Mixtures of the above may be used. The nitrogen-containing monomer is preferably used, for example, in an amount ranging from about 5 to about 95 percent based on the total weight of the monomers, and more preferably from about 15 to about 80 percent by weight.
Known and conventional protective colloids may be employed in the emulsion polymer such as partially and fully hydrolyzed polyvinyl alcohols; cellulose, ethers, e.g., hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, starch ad start derivatives, carboxymethyl cellulose (CMC); the natural and synthetic gums, e.g., gum tragacanth and gum Arabic, polyacrylic acid; acrylates; poly(vinyl alcohol)co(vinyl amine) copolymers and the like. Partially and fully hydrolyzed polyvinyl alcohols such as those available from Air Products, sold under the trademark Airvol™ are preferred and are preferably employed from about 0.1 to about 10 percent based on the weight of the total monomer, more preferably from about 0.5 to 5 percent, and most preferably from about 1 to about 4 percent.
In accordance with the invention, a polymerizable surfactant which contains ethylenic unsaturation is used and is copolymerized with the other monomers during emulsion polymerization. As a result, the surfactant is incorporated in to the backbone of the polymer and serves to stabilize the latex. Examples of suitable surfactants containing ethylenic unsaturation are provided in U.S. Pat. No. 5,296,627 to Tang et al., the disclosure of which is incorporated by reference herein in its entirety.
Various polymerizable surfactants are also described in U.S. Pat. No. 5,900,451 to Krishnan et al. A preferred polymerizable surfactant is SAM 186N™ sold by PPG Industries, Inc. of Pittsburgh, Pa. The polymerizable surfactant may be used in various amounts. Specifically, the stabilized emulsion polymer may include between about 0.1 and about 5 percent polymerizable surfactant based on the monomer weight, more preferably from about 1 to about 4 weight percent, and most preferably from about 2 to about 3 weight percent.
Conventional surfactants may be used in conjunction with the surfactant having ethylenic unsaturation described herein. Such surfactants are preferably of the anionic and nonionic type. The selection of these surfactants is apparent to one skilled in the art. Preferred nonionic surfactants are selected from the family of alkylphenoxypoly(ethyleneoxy) ethanols where the alkyl group typically various from C7-C18 and the ethylene oxide units vary from 4-100 moles. Various preferred surfactants in this class include the ethoxylated octyl and nonyl phenols, and in particular ethoxylated nonyl phenols with a hydrophobic/lipophilic balance (HLB) of 15-19. Non-APE (alkylphenol ethoxylate) surfactants such as ethoxylated alcohols, for example, Abex 2525, are also preferred. Anionic surfactants can be selected from the broad class of sulfonates, sulfates, ethersulfates, sulfosuccinates, diphenyloxide disulfonates, and the like, and are readily apparent to anyone skilled in the art.
An unsaturated mono- or dicarboxylic acid monomer may also be included in the stabilized emulsion polymer. These monomers include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. Derivatives, blends, and mixtures of the above may also be used. The unsaturated mono- or discarboxylic acid monomer may be used in an amount ranging from about 0 to about 15 percent based on the total monomer weight, and more preferably from about 0 to about 5 weight percent.
Additional comonomers can be added to the stabilized emulsion polymer. Included among such additional comonomers are monoethylenically unsaturated substituted aliphatic hydrocarbons such as vinyl chloride, and vinylidene chloride; aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl butyrate, vinyl versatate and vinyl neodecanoate.
The stabilized emulsion polymer can include additives to enhance its various physical and mechanical properties; the selection of which is readily apparent to one skilled in the art. For example, crosslinking agents can be included such as vinylic compounds (e.g., divinyl benzene); allyllic compounds (e.g., allyl methacrylate, diallyl maleate); multifunctional acrylates (e.g., di, tri and tetra (meth)acrylates); self-crosslinking monomers such as N-methylol acrylamide, N-methylol methacrylamide and C1 to C4 ethers of these monomers respectively (e.g., N-iso[butoxymethoxy] methacrylamide), acrylamido glycolic acid and its esters, and alkyl acrylamido glycolate alkyl ethers (e.g., methylacrylamido glycolate methyl ether). The crosslinking agents can be included in amounts of up to about 15 percent by weight, and preferably from about 3 to about 8 percent by weight. Additional monomers such as silanes can be included to improve specific properties such as latex stability, solvent resistance, as well as adhesion and strength and are described, for example, in U.S. Pat. No. 5,830,934 to Krishnan, the disclosure of which is incorporated herein by reference in its entirety.
Initiators which facilitate polymerization are typically used and include, for example, materials such as persulfates, organic peroxides, peresters, and azo compounds such as azobis(isobutyronitrile) (AIBN). Persulfate initiators are preferred and include, for example, potassium persulfate and ammonium persulfate.
Reductants may be employed in the polymerization, and are typically employed in combination with the initiator as part of a redox system. Suitable reductants include sodium bisulfite, erythorbic acid, ascorbic acid, sodium thiosulfate, sodium formaldehyde sulfoxylate (SFS), and the like.
Other additives which may be used include other natural and synthetic binders, fixing agents, wetting agents, plasticizers (e.g., diisodecyl phthalate), softeners, foam-inhibiting agents, froth aids, other crosslinking agents (e.g., melamine formaldehyde resin, epoxies, polyisocyanates, etc.), flame retardants, dispersing agents (e.g., tetrasodium pyrophosphate), pH adjusting components (e.g., ammonium hydroxide), sequestering or chelating agents (e.g., ethylene diaminetetraacetic acid (EDTA)) and other components. The selection of any of these additives is readily apparent to one skilled in the art.
One use of the reduced phenolic/butadiene blend is, for example, the fabrication of filters (e.g., oil filters). In the first or treating step, a continuous roll of paper is conventionally impregnated with the binder in the form of an alcohol solution. When a phenolic is used, the saturated paper is heated to remove the alcohol (solvent). In the present invention, the alcohol solution is not needed and this step is eliminated. The treated paper is then corrugated for the purpose of increasing surface area. The corrugated sheet is subsequently conveyed through an oven in order to advance the cure of the resinous impregnate to a fusible intermediate or B stage, and then the corrugated sheet is made into a filter.
The following examples are provided to illustrate the present invention, and should not be construed as limiting the scope thereof.
EXAMPLES Example 1
A polyvinyl alcohol stabilized butadiene emulsion is prepared comprising the following:
COMPONENT GRAMS
Deionized Water 2560.00
EDTA Chelating Agent 0.80
Dowfax 2A1 Surfactant 3.20
Airvol 103 PVOH 32.00
Abex 2525 Surfactant 16.00
Tamol 731A Dispersing Agent 0.80
Sam 186N Polymerizable Surfactant 16.00
Methoxy polyethylene 32.00
glycol methacrylate
Ammonium Persulfate Initiator 0.80
Butadiene 160.00
Tertiary Dodecyl Mercaptan 6.40
Acrylonitrile 320.00
Styrene 448.00
Acrylic Acid 16.00
Methylmethacrylate 480.00
Butylacrylate 80.00
N-methylol arylamide 64.00
Diammonium Phosphate 4.00
Wet performance testing was achieved by boiling the test samples in distilled water for 5 minutes. After the allocated time, the samples were removed and blotted dry but kept wet during testing by covering them with moist absorbent towels.
Tensile data was generated on substrate tested in the machine direction. Sample size was 1″×5″, with an extension rate of 10 inches/minute, and samples were tested on an Instron 1125.
The testing was done on No. 4 Whatman Filter Paper. Each sheet had a 20 percent add on of the composition of Example 1 is diluted to 22 percent total solids, was dried for 4 minutes at 225° F. and was allowed to condition overnight in a constant temperature/humidity room. Then each sheet was cured at 350° F. in a forced air oven for the cure times of the tables.
Max Load (lbf) Max Stn (elong) Max Str (psi)
Cure Time (std. dev.) (std. dev.) (std. dev.)
Example 1 - Wet Tensile Strength
1′ 11.97 (1.07) 4.027 (0.686) 25.75 (7.25)
2′ 13.14 (0.16) 4.210 (0.259) 27.52 (3.1) 
3′ 14.57 (0.47) 4.487 (0.105) 34.36 (1.25)
4′ 14.04 (0.52) 4.257 (0.229) 31.59 (3.17)
5′ 14.15 (0.63) 4.211 (0.298) 31.28 (4.50)
10′  13.77 (0.79) 3.846 (0.185) 27.01 (2.74)
Example 1 - Dry Tensile Strength
1′ 26.86 (1.57) 2.929 (0.259) 42.61 (9.17)
2′ 29.50 (1.22) 3.022 (0.183) 52.95 (4.99)
3′ 26.64 (1.17) 2.792 (0.229) 41.61 (6.13)
4′ 27.80 (2.03) 2.747 (0.396)  46.08 (11.37)
5′ 28.19 (0.68) 2.746 (0.258) 46.41 (6.43)
10′  26.83 (2.01) 2.471 (0.317) 38.80 (9.68)
Examples 2-7
Various amounts a phenolic available as Resafen 8121 from Resana, Sao Paulo Brazil, were added to Example 1, along with phenolic only, and the tensile strengths measured. The amounts added are as follows:
Example Amt (%) of Example 1 Amt (%) of Phenolic
2 98 2
3 96 4
4 94 6
5 92 8
6 90 10
7 50 50
8 0 100
The wet tensile strength results are as follows:
Example 2
Cure Time Max Load Max elong Max psi
% add-on @ 350 F. (std. dev.) (std. dev.) (std. dev.)
19.2 1′ 12.11 (0.38) 4.394 (0.002) 27.12 (1.40)
19.2 2′ 14.84 (0.19) 4.669 (0.105) 36.66 (1.29)
19.2 3′ 15.00 (0.81) 4.441 (0.311) 34.61 (4.06)
19.6 4′ 14.28 (0.44) 4.393 (0.183) 32.35 (2.13)
19.6 5′ 14.38 (0.57) 4.396 (0.183) 32.89 (2.77)
19.6 10′  14.26 (0.58) 3.967 (0.107) 29.32 (1.75)
Example 3
Cure Time Max Load Max elong Max psi
% add-on @ 350 F. (std. dev.) (std. dev.) (std. dev.)
19.9 1′ 14.12 (0.12) 4.821 (0.28)  36.62 (2.32)
19.9 2′ 15.38 (1.14) 4.898 (0.345) 39.14 (6.60)
19.9 3′ 14.88 (0.27) 4.271 (0.106) 31.13 (0.99)
19.4 4′ 16.35 (1.40) 4.454 (0.529) 38.14 (7.74)
19.4 5′ 16.33 (0.83) 4.303 (0.184) 36.45 (5.24)
19.4 10′  16.11 (0.81) 4.027 (0.258) 31.90 (4.20)
Example 4
Cure Time Max Load Max elong Max psi
% add-on @ 350 F. (std. dev.) (std. dev.) (std. dev.)
19.4 1′ 14.00 (0.55) 4.897 (0.311) 36.02 (3.47)
19.4 2′ 17.65 (0.97) 5.081 (0.406) 45.86 (6.85)
19.4 3′ 17.52 (0.83) 4.806 (0.433) 43.47 (5.51)
19.3 4′ 19.10 (0.93) 4.822 (0.280) 47.26 (4.76)
19.3 5′ 18.50 (0.71) 4.577 (0.183) 43.58 (3.37)
19.3 10′  19.14 (1.10) 4.347 (0.313) 41.73 (4.38)
Example 5
Cure Time Max Load Max elong Max psi
% add-on @ 350 F. (std. dev.) (std. dev.) (std. dev.)
19.4 1′ 13.35 (1.08) 4.578 (0.539) 32.29 (6.96)
19.4 2′ 18.63 (0.50) 5.172 (0.175) 49.29 (3.15)
19.4 3′ 19.49 (0.95) 4.898 (0.405) 48.49 (5.48)
19.8 4′ 20.02 (0.72) 4.668 (0.317) 48.06 (4.52)
19.8 5′ 22.05 (0.70) 4.943 (0.335) 57.85 (5.97)
19.8 10′  20.79 (1.49) 4.531 (0.347) 48.06 (8.20)
Example 6
Cure Time Max Load Max elong Max psi
% add-on @ 350 F. (std. dev.) (std. dev.) (std. dev.)
19.5 1′ 15.84 (0.45) 5.127 (0.259)  42.05 (0.281)
19.5 2′ 19.36 (0.62) 5.188 (0.212) 50.93 (4.13)
19.5 3′ 20.16 (1.05) 4.623 (0.231) 48.82 (5.46)
19.3 4′ 22.59 (0.69) 5.188 (0.212) 60.15 (3.89)
19.3 5′ 23.05 (0.93) 4.852 (0.235) 58.31 (5.02)
19.3 10′  22.55 (0.86) 4.578 (0.150) 54.30 (3.40)
Example 7
Cure Time Max Load Max elong Max psi
% add-on @ 350 F. (std. dev.) (std. dev.) (std. dev.)
19.9 1′ 13.84 (0.99) 5.035 (0.57)  33.45 (4.27)
19.9 2′ 21.98 (0.85) 4.669 (0.235) 54.29 (5.16)
19.9 3′ 23.79 (1.74) 4.073 (0.347) 52.04 (9.66)
20.1 4′ 26.68 (0.78) 3.891 (0.229) 57.95 (4.95)
20.1 5′ 15.26 (0.45) 3.526 (0.092) 49.22 (2.34)
20.1 10′  26.06 (2.42) 3.066 (0.525)  44.42 (11.01)
Example 8
Pro- Cure Time Max Load Max elong Max psi
duct @ 350 F. (std. dev.) (std. dev.) (std. dev.)
Re- 1′   11.72 (1.6.29) 1.466 (0.185) 6.711 (2.118)
safen 2′ 13.11 (1.11) 1.190 (0.132) 6.031 (0.937)
8121 3′ 13.00 (0.70) 1.283 (0.00)  5.490 (0.509)
4′ 9.7222 (1.440) 0.9778 (0.1058) 2.622 (0.618)
5′ 12.24 (1.05) 1.097 (0.183) 4.955 (0.621)
10′  12.05 (0.73) 1.160 (0.104) 4.533 (0.598)
Example 9
A polyvinyl alcohol stabilized emulsion having more N-methylol acrylamide and no butylacrylate is prepared, comprising the following:
COMPONENT GRAMS
Deionized Water 2560.00
EDTA Chelating Agent 0.80
Dowfax 2A1 Surfactant 3.20
Airvol 103 PVOH 32.00
Abex 2525 Surfactant 16.00
Tamol 731A Dispersing Agent 0.80
Sam 186N Polymerizable Surfactant 16.00
Methoxy polyethylene 32.00
glycol methacrylate
Ammonium Persulfate Initiator 0.80
Butadiene 240.00
Tertiary Dodecyl Mercaptan 6.40
Acrylonitrile 320.00
Styrene 704.00
Acrylic Acid 16.00
Methylmethacrylate 176.00
N-methylol arylamide 112.00
Diammonium Phosphate 4.00
The wet tensile strength at different cure rates was as follows:
Cure Time 350° F. Lbf (std. dev.) Elong (std. dev.) Psi (std. dev.)
1′ 17.41 (0.42  5.310 (0.299) 45.57 (4.37)
2′ 17.58 (1.08) 5.004 (0.212) 44.59 (6.09)
3′ 17.47 (0.93) 4.822 (0.279) 41.23 (5.58)
4′ 16.89 (0.32) 4.699 (0.106) 38.49 (2.96)
5′ 17.32 (0.62) 4.699 (0.212) 40.55 (2.73)
10′  16.99 (0.58) 4.393 (0.183) 38.19 (2.37)
The above examples illustrate that compositions having no phenolic or reduced phenolic can provide physical properties comparable to conventional emulsion compositions having phenolics.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof. Although a few exemplary embodiments of this invention have been described, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the claims. Therefore, it is to be understood that the foregoing is illustrative of the present invention and is not to be construed as limited to the specific embodiments disclosed, and that modifications to the disclosed embodiments, as well as other embodiments, are intended to be included within the scope of the appended claims. The invention is defined by the following claims, with equivalents of the claims to be included therein.

Claims (7)

That which is claimed is:
1. A filter comprising a filter substrate impregnated with polymer in emulsion form selected from the group consisting of vinyl acrylates, epoxies, urethanes, acrylics, styrene acrylics, butadiene copolymers and hybrid emulsions of combinations thereof, the polymer having crosslinkable functionality being substantially devoid of phenolics and provided by a self-crosslinking monomer selected from the group consisting of N-methylol acrylamide, N-methylol methacrylamide and C1 to C4 ethers thereof, and stabilized using a protective colloid.
2. The filter according to claim 1, wherein the protective colloid is a polyvinyl alcohol.
3. The filter according to claim 2, wherein the polyvinyl alcohol is fully hydrolyzed.
4. The filter according to claim 2, wherein the polyvinyl alcohol is partially hydrolyzed.
5. A filter comprising a filter substrate impregnated with polymer in emulsion form selected from the group consisting of vinyl acrylates, epoxies, urethanes, acrylics, styrene acrylics, butadiene copolymers and hybrid emulsions of combinations thereof, the polymer having crosslinkable functionality being substantially devoid of phenolics and provided by a self-crosslinking monomer selected from the group consisting of N-methylol acrylamide, N-methylol methacrylamide and C1 to C4 ethers thereof, and stabilized using a polyvinyl alcohol.
6. The filter according to claim 5, wherein polyvinyl alcohol is fully hydrolyzed.
7. The filter according to claim 5, wherein the polyvinyl alcohol is partially hydrolyzed.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304693C (en) * 2005-01-04 2007-03-14 浙江大学 Automobile engine filter paper immersion resin emusion and preparation method thereof
US20100018533A1 (en) * 2006-07-18 2010-01-28 Kimberly Biedermann Novel Device
CN101230553B (en) * 2008-01-08 2011-08-17 牡丹江恒丰纸业股份有限公司 Automobile industry filter paper impregnation emulsion and method for modifying the same by using polymerizable emulsifier
US10918976B2 (en) * 2018-10-24 2021-02-16 Pall Corporation Support and drainage material, filter, and method of use

Citations (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1265549A (en) 1959-08-01 1961-06-30 Hoechst Ag Process for preparing dispersions of polymerizates
US3365408A (en) 1963-08-12 1968-01-23 Kurashiki Rayon Co Adhesives comprising polyvinyl alcohol bearing or mixed with substances bearing carboxyl groups, and a stabilizer
US4045398A (en) 1975-11-24 1977-08-30 Monsanto Company Resole resin binder composition
US4170582A (en) 1976-08-03 1979-10-09 Dainippon Ink And Chemicals, Inc. Process for preparing a polymer resin aqueous dispersion
US4179537A (en) 1978-01-04 1979-12-18 Rykowski John J Silane coupling agents
US4257935A (en) 1975-11-28 1981-03-24 Sumitomo Naugatuck Co., Ltd. Color developing sheet for pressure-sensitive recording systems
US4265796A (en) 1978-09-30 1981-05-05 Basf Aktiengesellschaft Preparation of aqueous polyacrylate dispersions having improved flow characteristics
US4287329A (en) 1979-01-22 1981-09-01 National Distillers And Chemical Corp. Emulsion process for preparing elastomeric vinyl acetate-ethylene copolymer and high Mooney viscosity low gel content elastomer obtained therefrom
US4336172A (en) 1979-07-02 1982-06-22 Wacker-Chemie Gmbh Aqueous dispersions of cross-linkable copolymers based on (meth)acrylates, their preparation and use as stoving enamels
US4339552A (en) 1978-09-18 1982-07-13 National Starch & Chemical Corporation Vinyl ester aqueous adhesive emulsions including acrylamide
JPS57180061A (en) 1981-04-16 1982-11-05 Philips Nv Reflector lamp and method of producing same
GB2099000A (en) 1981-04-06 1982-12-01 Badische Yuka Co Ltd Inorganic filler-containing vinyl monomer compositions and process for the production therefrom of polymer particles
US4384096A (en) 1979-08-27 1983-05-17 The Dow Chemical Company Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems
US4384661A (en) 1982-04-07 1983-05-24 Page Edward H Aerosol water-based paint compositions
US4397968A (en) 1981-03-24 1983-08-09 Wacker-Chemie Gmbh Process for the manufacture of copolymers having increased resistance against hydrolysis, the copolymers and their use
US4417016A (en) 1982-02-19 1983-11-22 Para-Chem Southern, Inc. Frothing aid composition
US4477613A (en) 1983-08-01 1984-10-16 Sylvachem Corporation Stabilization of tackifying resin dispersions
US4495329A (en) 1983-03-28 1985-01-22 Georgia-Pacific Resins, Inc. Phenolic resin compounds
US4510019A (en) 1981-05-12 1985-04-09 Papeteries De Jeand'heurs Latex containing papers
US4528315A (en) 1982-07-20 1985-07-09 Wacker-Chemie Gmbh Process for the preparation of polymer dispersions and their application
US4623462A (en) 1984-10-29 1986-11-18 The Bf Goodrich Company Oil filters using water-based latex binders
US4670181A (en) 1984-06-25 1987-06-02 The B. F. Goodrich Company Process for pelletization of powder materials and products therefrom
JPH0228203A (en) 1988-07-15 1990-01-30 Showa Highpolymer Co Ltd Polyvinyl acetate-based emulsion composition
US4904753A (en) 1988-03-23 1990-02-27 Ashland Oil, Inc. Acid/oxidizer catalyst system for storage stable, quick-cure phenolic resins of the resole or benzylic ether resole type
US4937284A (en) 1983-02-17 1990-06-26 Neste Oy Modified polyolefin, method for making the same, and use thereof
JPH02196880A (en) 1989-01-25 1990-08-03 Sekisui Chem Co Ltd Tacky adhesive composition
US4999239A (en) 1989-03-20 1991-03-12 Air Products And Chemicals, Inc. Ethylene-vinyl chloride copolymer emulsions containing tetramethylol glycoluril for use as binder compositions
US5001011A (en) 1988-06-03 1991-03-19 Dow Corning Corporation Ionomeric silane coupling agents
US5006573A (en) 1985-11-29 1991-04-09 Dow Corning Corporation Silane coupling agents
US5100948A (en) 1988-10-14 1992-03-31 Basf Aktiengesellschaft Aqueous formulations suitable as sealing compounds of adhesives for ceramic tiles
US5141983A (en) 1988-05-30 1992-08-25 Dainippon Ink & Chemicals, Inc. Aqueous coating composition
US5155193A (en) 1990-07-02 1992-10-13 Xerox Corporation Suspension polymerization processes
EP0516360A1 (en) 1991-05-31 1992-12-02 Lord Corporation Stable butadiene polymer latices
US5190997A (en) * 1985-07-10 1993-03-02 Sequa Chemicals, Inc. Adhesive composition
JPH0559106A (en) 1991-09-03 1993-03-09 Kuraray Co Ltd Dispersion stabilizer for emulsion polymerization
US5200459A (en) 1991-05-31 1993-04-06 Lord Corporation Stable butadiene heteropolymer latices
US5244695A (en) 1992-03-17 1993-09-14 Air Products And Chemicals, Inc. Aqueous binder saturants used in a process for making nonwoven filters
US5296627A (en) 1988-06-20 1994-03-22 Ppg Industries, Inc. Ethylenically unsaturated poly(alkyleneoxy) surfactants
US5300555A (en) 1991-05-31 1994-04-05 Lord Corporation Stable butadiene homopolymers latices
US5308910A (en) 1991-06-25 1994-05-03 Kuraray Co., Ltd. Composition, adhesive and aqueous emulsion
JPH06128443A (en) 1992-10-21 1994-05-10 Kuraray Co Ltd Aqueous emulsion
JPH06179705A (en) 1992-12-15 1994-06-28 Kuraray Co Ltd Emulsifying and dispersion-stabilizing agent
US5352720A (en) 1992-04-29 1994-10-04 Basf Aktiengesellschaft Aqueous polymer dispersion containing a polydisperse particle size distribution
US5354803A (en) 1993-03-29 1994-10-11 Sequa Chemicals, Inc. Polyvinyl alcohol graft copolymer nonwoven binder emulsion
US5385973A (en) 1987-12-17 1995-01-31 Vedril S.P.A. Process for preparing flowable, stable and hardenable suspensions, and thus-obtained compositions
EP0640629A1 (en) 1993-08-30 1995-03-01 Hüls Aktiengesellschaft Process for the preparation of aquous silanol groups modified plastics
JPH0770989A (en) 1993-08-23 1995-03-14 Kuraray Co Ltd Emulsion for paper coating
US5428095A (en) 1992-06-09 1995-06-27 Cal-West Automotive Protective coating composition and method of using such composition
US5434216A (en) 1993-05-07 1995-07-18 National Starch And Chemical Investment Holding Corporation Woodworking latex adhesives with improved water, heat and creep resistance
CA2182202A1 (en) 1994-01-27 1995-08-03 Herbert Eck Redispersible silicon-modified dispersion powder composition, method of manufacturing it and its use
US5444112A (en) 1994-05-16 1995-08-22 Cj's Distributing, Inc. Sprayable nonionic neoprene latex adhesive and method of preparation
US5451635A (en) 1992-04-23 1995-09-19 Rohm And Haas Company Polymer blends
US5461104A (en) 1994-01-21 1995-10-24 Shell Oil Company Process for making water-based latexes of block copolymers
US5470924A (en) 1991-04-05 1995-11-28 Ryan; Barry W. Phenol formaldehyde resins
US5491209A (en) 1989-10-25 1996-02-13 The Dow Chemical Company Latex copolymers for paper coating compositions
US5496884A (en) 1993-11-12 1996-03-05 Lord Corporation Aqueous adhesive for bonding elastomers
US5502089A (en) 1993-08-27 1996-03-26 Rohm And Haas Company Polymer emulsion agent for cross-linking a polymer emulsion and method for making a polymer film
US5519084A (en) 1992-12-08 1996-05-21 Air Products And Chemicals, Inc. Redispersible acrylic polymer powder for cementitious compositions
US5520997A (en) 1994-11-17 1996-05-28 The B. F. Goodrich Company Formaldehyde-free latex for use as a binder or coating
US5539015A (en) 1991-07-25 1996-07-23 Kabushiki Kaisha Toyota Chuo Kenkyusho Synthetic resin composition and interior material coated with the same
US5629370A (en) 1996-04-29 1997-05-13 Reichhold Chemicals, Inc. High solids vinyl acetate-ethylene emulsions
US5830934A (en) 1995-10-27 1998-11-03 Reichhold Chemicals, Inc. Colloidally stabilized emulsion polymer
US5900451A (en) 1997-05-15 1999-05-04 Reichhold Chemicals, Inc. Collaidally stabilized butadiene emulsions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57180617A (en) 1981-05-01 1982-11-06 Japan Synthetic Rubber Co Ltd Copolymer latex for chipping-resistant paint
DE19633626A1 (en) * 1996-08-21 1998-02-26 Basf Ag Process for producing a particulate polymer

Patent Citations (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1265549A (en) 1959-08-01 1961-06-30 Hoechst Ag Process for preparing dispersions of polymerizates
US3365408A (en) 1963-08-12 1968-01-23 Kurashiki Rayon Co Adhesives comprising polyvinyl alcohol bearing or mixed with substances bearing carboxyl groups, and a stabilizer
US4045398A (en) 1975-11-24 1977-08-30 Monsanto Company Resole resin binder composition
US4257935A (en) 1975-11-28 1981-03-24 Sumitomo Naugatuck Co., Ltd. Color developing sheet for pressure-sensitive recording systems
US4170582A (en) 1976-08-03 1979-10-09 Dainippon Ink And Chemicals, Inc. Process for preparing a polymer resin aqueous dispersion
US4179537A (en) 1978-01-04 1979-12-18 Rykowski John J Silane coupling agents
US4339552A (en) 1978-09-18 1982-07-13 National Starch & Chemical Corporation Vinyl ester aqueous adhesive emulsions including acrylamide
US4265796A (en) 1978-09-30 1981-05-05 Basf Aktiengesellschaft Preparation of aqueous polyacrylate dispersions having improved flow characteristics
US4287329A (en) 1979-01-22 1981-09-01 National Distillers And Chemical Corp. Emulsion process for preparing elastomeric vinyl acetate-ethylene copolymer and high Mooney viscosity low gel content elastomer obtained therefrom
US4336172A (en) 1979-07-02 1982-06-22 Wacker-Chemie Gmbh Aqueous dispersions of cross-linkable copolymers based on (meth)acrylates, their preparation and use as stoving enamels
US4384096A (en) 1979-08-27 1983-05-17 The Dow Chemical Company Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems
US4397968A (en) 1981-03-24 1983-08-09 Wacker-Chemie Gmbh Process for the manufacture of copolymers having increased resistance against hydrolysis, the copolymers and their use
GB2099000A (en) 1981-04-06 1982-12-01 Badische Yuka Co Ltd Inorganic filler-containing vinyl monomer compositions and process for the production therefrom of polymer particles
JPS57180061A (en) 1981-04-16 1982-11-05 Philips Nv Reflector lamp and method of producing same
US4510019A (en) 1981-05-12 1985-04-09 Papeteries De Jeand'heurs Latex containing papers
US4417016A (en) 1982-02-19 1983-11-22 Para-Chem Southern, Inc. Frothing aid composition
US4384661A (en) 1982-04-07 1983-05-24 Page Edward H Aerosol water-based paint compositions
US4528315A (en) 1982-07-20 1985-07-09 Wacker-Chemie Gmbh Process for the preparation of polymer dispersions and their application
US4937284A (en) 1983-02-17 1990-06-26 Neste Oy Modified polyolefin, method for making the same, and use thereof
US4495329A (en) 1983-03-28 1985-01-22 Georgia-Pacific Resins, Inc. Phenolic resin compounds
US4477613A (en) 1983-08-01 1984-10-16 Sylvachem Corporation Stabilization of tackifying resin dispersions
US4670181A (en) 1984-06-25 1987-06-02 The B. F. Goodrich Company Process for pelletization of powder materials and products therefrom
US4623462A (en) 1984-10-29 1986-11-18 The Bf Goodrich Company Oil filters using water-based latex binders
US5190997A (en) * 1985-07-10 1993-03-02 Sequa Chemicals, Inc. Adhesive composition
US5006573A (en) 1985-11-29 1991-04-09 Dow Corning Corporation Silane coupling agents
US5385973A (en) 1987-12-17 1995-01-31 Vedril S.P.A. Process for preparing flowable, stable and hardenable suspensions, and thus-obtained compositions
US4904753A (en) 1988-03-23 1990-02-27 Ashland Oil, Inc. Acid/oxidizer catalyst system for storage stable, quick-cure phenolic resins of the resole or benzylic ether resole type
US5141983A (en) 1988-05-30 1992-08-25 Dainippon Ink & Chemicals, Inc. Aqueous coating composition
US5001011A (en) 1988-06-03 1991-03-19 Dow Corning Corporation Ionomeric silane coupling agents
US5296627A (en) 1988-06-20 1994-03-22 Ppg Industries, Inc. Ethylenically unsaturated poly(alkyleneoxy) surfactants
JPH0228203A (en) 1988-07-15 1990-01-30 Showa Highpolymer Co Ltd Polyvinyl acetate-based emulsion composition
US5100948A (en) 1988-10-14 1992-03-31 Basf Aktiengesellschaft Aqueous formulations suitable as sealing compounds of adhesives for ceramic tiles
JPH02196880A (en) 1989-01-25 1990-08-03 Sekisui Chem Co Ltd Tacky adhesive composition
US4999239A (en) 1989-03-20 1991-03-12 Air Products And Chemicals, Inc. Ethylene-vinyl chloride copolymer emulsions containing tetramethylol glycoluril for use as binder compositions
US5491209A (en) 1989-10-25 1996-02-13 The Dow Chemical Company Latex copolymers for paper coating compositions
US5155193A (en) 1990-07-02 1992-10-13 Xerox Corporation Suspension polymerization processes
US5470924A (en) 1991-04-05 1995-11-28 Ryan; Barry W. Phenol formaldehyde resins
US5200459A (en) 1991-05-31 1993-04-06 Lord Corporation Stable butadiene heteropolymer latices
US5300555A (en) 1991-05-31 1994-04-05 Lord Corporation Stable butadiene homopolymers latices
EP0516360A1 (en) 1991-05-31 1992-12-02 Lord Corporation Stable butadiene polymer latices
US5308910A (en) 1991-06-25 1994-05-03 Kuraray Co., Ltd. Composition, adhesive and aqueous emulsion
US5539015A (en) 1991-07-25 1996-07-23 Kabushiki Kaisha Toyota Chuo Kenkyusho Synthetic resin composition and interior material coated with the same
JPH0559106A (en) 1991-09-03 1993-03-09 Kuraray Co Ltd Dispersion stabilizer for emulsion polymerization
US5244695A (en) 1992-03-17 1993-09-14 Air Products And Chemicals, Inc. Aqueous binder saturants used in a process for making nonwoven filters
US5451635A (en) 1992-04-23 1995-09-19 Rohm And Haas Company Polymer blends
US5352720A (en) 1992-04-29 1994-10-04 Basf Aktiengesellschaft Aqueous polymer dispersion containing a polydisperse particle size distribution
US5428095A (en) 1992-06-09 1995-06-27 Cal-West Automotive Protective coating composition and method of using such composition
JPH06128443A (en) 1992-10-21 1994-05-10 Kuraray Co Ltd Aqueous emulsion
US5519084A (en) 1992-12-08 1996-05-21 Air Products And Chemicals, Inc. Redispersible acrylic polymer powder for cementitious compositions
JPH06179705A (en) 1992-12-15 1994-06-28 Kuraray Co Ltd Emulsifying and dispersion-stabilizing agent
WO1994022671A1 (en) 1993-03-29 1994-10-13 Sequa Chemicals, Inc. A polyvinyl alcohol graft copolymer non-woven binder emulsion
US5354803A (en) 1993-03-29 1994-10-11 Sequa Chemicals, Inc. Polyvinyl alcohol graft copolymer nonwoven binder emulsion
US5434216A (en) 1993-05-07 1995-07-18 National Starch And Chemical Investment Holding Corporation Woodworking latex adhesives with improved water, heat and creep resistance
JPH0770989A (en) 1993-08-23 1995-03-14 Kuraray Co Ltd Emulsion for paper coating
US5502089A (en) 1993-08-27 1996-03-26 Rohm And Haas Company Polymer emulsion agent for cross-linking a polymer emulsion and method for making a polymer film
EP0640629A1 (en) 1993-08-30 1995-03-01 Hüls Aktiengesellschaft Process for the preparation of aquous silanol groups modified plastics
US5496884A (en) 1993-11-12 1996-03-05 Lord Corporation Aqueous adhesive for bonding elastomers
US5461104A (en) 1994-01-21 1995-10-24 Shell Oil Company Process for making water-based latexes of block copolymers
CA2182202A1 (en) 1994-01-27 1995-08-03 Herbert Eck Redispersible silicon-modified dispersion powder composition, method of manufacturing it and its use
US5444112A (en) 1994-05-16 1995-08-22 Cj's Distributing, Inc. Sprayable nonionic neoprene latex adhesive and method of preparation
US5520997A (en) 1994-11-17 1996-05-28 The B. F. Goodrich Company Formaldehyde-free latex for use as a binder or coating
US5830934A (en) 1995-10-27 1998-11-03 Reichhold Chemicals, Inc. Colloidally stabilized emulsion polymer
US5629370A (en) 1996-04-29 1997-05-13 Reichhold Chemicals, Inc. High solids vinyl acetate-ethylene emulsions
US5900451A (en) 1997-05-15 1999-05-04 Reichhold Chemicals, Inc. Collaidally stabilized butadiene emulsions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Yuki et al; "The Role of Polyvinyl Alcohol in Emulsion Polymerization", Polymer International 30:4 513-517 (1993).

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304693C (en) * 2005-01-04 2007-03-14 浙江大学 Automobile engine filter paper immersion resin emusion and preparation method thereof
US20100018533A1 (en) * 2006-07-18 2010-01-28 Kimberly Biedermann Novel Device
CN101230553B (en) * 2008-01-08 2011-08-17 牡丹江恒丰纸业股份有限公司 Automobile industry filter paper impregnation emulsion and method for modifying the same by using polymerizable emulsifier
US10918976B2 (en) * 2018-10-24 2021-02-16 Pall Corporation Support and drainage material, filter, and method of use

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